EP0327576B1 - Verfahren zur herstellung von zellstoff aus ligninhaltigen rohstoffen - Google Patents

Verfahren zur herstellung von zellstoff aus ligninhaltigen rohstoffen Download PDF

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Publication number
EP0327576B1
EP0327576B1 EP87907315A EP87907315A EP0327576B1 EP 0327576 B1 EP0327576 B1 EP 0327576B1 EP 87907315 A EP87907315 A EP 87907315A EP 87907315 A EP87907315 A EP 87907315A EP 0327576 B1 EP0327576 B1 EP 0327576B1
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EP
European Patent Office
Prior art keywords
lignin
process according
reaction
redox potential
enzyme
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EP87907315A
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German (de)
English (en)
French (fr)
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EP0327576A1 (de
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Hans-Peter Dr. Call
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/22—Other features of pulping processes
    • D21C3/228—Automation of the pulping processes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
    • D21C5/005—Treatment of cellulose-containing material with microorganisms or enzymes

Definitions

  • the invention relates to a method for removing and / or converting lignin from lignocellulose-containing material.
  • the lingocellulose-containing material such as wood or annual plants, must be freed from the lignin, since this considerably improves the mechanical and physicochemical properties of the paper produced from the cellulose.
  • Conventional processes work with high pressures and temperatures using environmentally harmful chemicals.
  • P.J. Harvey et al examined the role of radical cations in the breakdown of lignin. They have observed that veratryl alcohol can act as a mediator in the in-vivo process for lignin degradation using Phanerochaete chrysosporium (Abstract Bulletin of the Institute of Paper Chemistry, Volume 57, No. 7, January 1987, Appieton, Wisconsin, USA) P.J. Harvey et al: "Lignin-degrading enzymes and the role of radical cations in lignin biodegradation", see page 958, summary 8575, & STFI / SPCI Int. Conf. Biotechnol. Pulp & Paper Ind.
  • Phanerochaete chrysosporium produces a peroxidase, which causes the oxidation of manganese (II) to manganese (III).
  • the manganese (III) in turn causes the oxidation of the lignin molecules.
  • Mn peroxidase production plays a crucial role in the degradation of lignin.
  • “Paszczgnski, A. et al .:” Composition of Ligninase-l and Peroxidase-M2 from the White-Red Fungus Phanerochaete chrysosporium. Arch. Biochem. Biophys. Vol. 244. No. 2 "that the addition of reducing agents inhibits the Mn-dependent peroxidase of Phanerochaete chrysosporium. Dithionite, on the other hand, acts as an activator.
  • veratryl alcohol only serves to promote the formation of lignin-degrading enzymes.
  • the present invention has now set itself the task of a method for removing and / or converting lignin or its degradation products from lignocellulose-containing material with the aid of lignolytic enzymes obtained, in which the disadvantages of the use of microorganisms, enzymes and chemicals shown above are avoided, to provide.
  • This object is achieved in that a) by adding oxidizing agents, reducing agents, salts and phenolic compounds to an aqueous solution of the lignin-containing raw materials, a redox potential in the range from 200 to 500 mV is set, b) subsequently adding a lignin-degrading reaction by adding the lignolytic enzymes simultaneous bleaching started, c) the reaction at a value between 200 and 500 mV, constant temperature between 20 and 60 ° C, constant pH between 2 and 5 and maintained with constant stirring for 2 to 6 hours d) the redox potential is continuously determined by means of a redox electrode and by means of a regulator and actuator during the entire reaction by adding oxidizing agents. Reducing agents, salts, phenolic compounds and organic acids are kept between 200 and 500 mV and e) after the end of the reaction, the enzyme is passed over a separation column, purified there and returned to the reaction process.
  • the redox potential is preferably 250 to 350 mV. Hydrogen peroxide, oxygen and ozone are preferably used as the oxidizing agent. Ascorbic acid, dithionite and sodium bisulfite are suitable as reducing agents. MnSO4 and / or FeCl2 is preferably suitable as the salt. Veratryl alcohol can be used as the phenolic compound. The organic acid comes e.g. Lactic acid into consideration.
  • Lignolytic enzymes are preferably used as enzymes in the method according to the invention. These preferably include phenol oxidases, laccases and peroxidases.
  • the effectiveness of the method according to the invention can be increased by adding pectinases and / or hemicellulases.
  • the pH in the process according to the invention is between 2 and 5. A pH of 3 is particularly preferred.
  • the temperature is 20 to 60 ° C.
  • the reaction is preferably carried out at 40 ° C.
  • a redox potential of 250-350 mV can be set.
  • the lignin content of wheat straw (approx. 18% lignin content) can be reduced to almost 0%.
  • Spruce wood (about 28-30% lignin content) can be broken down to similar end values.
  • these results can be achieved in 2 to 6 hours, in many cases even within 2 hours. This does not include the physical and / or chemical pretreatment that is particularly necessary when using wood or annual plants.
  • the redox potential is set by the ratio of the various substances added in the reaction vessel. By measuring and controlling the addition of the oxidizing and reducing agents, the salts, the phenolic compounds and organic acids, a certain redox potential can be maintained throughout the course of the reaction.
  • the aim of the operation of the redox system set in this way is to intercept the radicals arising in the oxidation reaction and thus to prevent the repolymerization of the lignin.
  • the process also has a significant bleaching effect during the degradation and / or conversion reaction, which allows it to be done with significantly less pollution Bleach to work.
  • the process according to the invention is therefore also suitable as a bleaching or post-bleaching process for various processes.
  • the process can therefore also be used for the biological bleaching and biological wastewater treatment of pulp industry wastewater and other wastewater.
  • the method can be used wherever decolorization and detoxification of waste water is to be achieved.
  • Another advantage of the process according to the invention is the possibility of continuous process control.
  • the process can be carried out particularly economically if the used enzymes are reprocessed and returned to the reaction process. This goal can be achieved with the help of affinity chromatography.
  • the enzyme is passed over a separation column, purified there and returned to the reaction process.
  • the enzyme purification is carried out in the separation column by means of affinity chromatography.
  • affinity chromatography For this purpose, new specific types of ligands have been developed, which are used together with the corresponding enzyme technology know-how.
  • phenolic compounds can be used here.
  • Protein-specific ligands are also suitable. Tannin is an example.
  • Microorganisms or enzymes are added to the reactor via the inflow 7.
  • the microorganisms or enzymes can optionally also be immobilized in the reactor.
  • Conventional fillers and carriers can be used for the immobilization.
  • Oxidizing agents, reducing agents, salts or phenolic compounds can be metered in via the inflow 4.
  • the dosage can be controlled depending on the respective redox potential.
  • a redox electrode must be attached to the reactor (not shown in the picture), by means of which the redox potential is continuously determined. By connecting to an appropriate control system, the redox potential can then be kept constant during the entire course of the reaction.
  • the raw materials are also added via the feed line 7.
  • chemically and / or physically pretreated straw and wood come into consideration.
  • Lignin and waste water containing lignin can also be treated in the plant according to the invention.
  • the lignin is broken down in the reactor with the aid of lignolytic enzymes or microorganisms.
  • Particularly suitable enzymes are those which have been obtained from the fungus Phanerochaete chrysosporium. Cellulase- and hemicellulase-free mutants are particularly suitable as microorganisms.
  • mutants of Phanerochaete chrysosporium can be used.
  • the converted raw material flows out of the reactor via the drain 8 together with the used chemicals, microorganisms or enzymes.
  • the mixture of substances is passed, for example, through a filter 3, where dissolved and undissolved substances are separated from one another.
  • the enzyme-containing solution is passed through a chromatography column 2. This column works on the principle of affinity chromatography. Here the enzymes are reprocessed and then fed back to the reaction process via line 5.
  • the substances separated from the enzymes are discharged via line 6.
  • Special enzyme-specific ligands, in particular phenolic compounds are used for affinity chromatography. Protein-specific ligands, in particular tannin, can also be used.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Microbiology (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Paper (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Compounds Of Unknown Constitution (AREA)
  • Enzymes And Modification Thereof (AREA)
  • Processing Of Solid Wastes (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
  • Audible-Bandwidth Dynamoelectric Transducers Other Than Pickups (AREA)
EP87907315A 1986-10-24 1987-10-24 Verfahren zur herstellung von zellstoff aus ligninhaltigen rohstoffen Expired - Lifetime EP0327576B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87907315T ATE86318T1 (de) 1986-10-24 1987-10-24 Verfahren zur herstellung von zellstoff aus ligninhaltigen rohstoffen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3636208 1986-10-24
DE19863636208 DE3636208A1 (de) 1986-10-24 1986-10-24 Verfahren zur delignifizierung und bleichung von lignicellulosehaltigem bzw. ligninhaltigem material bzw. lignin durch enzymatische behandlung

Publications (2)

Publication Number Publication Date
EP0327576A1 EP0327576A1 (de) 1989-08-16
EP0327576B1 true EP0327576B1 (de) 1993-03-03

Family

ID=6312392

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87907315A Expired - Lifetime EP0327576B1 (de) 1986-10-24 1987-10-24 Verfahren zur herstellung von zellstoff aus ligninhaltigen rohstoffen

Country Status (11)

Country Link
EP (1) EP0327576B1 (ja)
JP (1) JPH0718108B2 (ja)
AT (1) ATE86318T1 (ja)
AU (1) AU605215B2 (ja)
BR (1) BR8707844A (ja)
DE (2) DE3636208A1 (ja)
DK (1) DK170810B1 (ja)
FI (1) FI95289C (ja)
HU (2) HU202938B (ja)
NO (1) NO175104C (ja)
WO (1) WO1988003190A1 (ja)

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA894239B (en) * 1988-06-08 1990-03-28 Int Paper Co Enzymatic delignification of lignocellulosic material
FI88316C (fi) * 1989-07-10 1993-04-26 Enso Gutzeit Oy Foerfarande foer blekning av cellulosamassa
NO178201C (no) * 1989-09-12 1996-02-07 Sandoz Ag Ligninnedbrytende enzymatisk preparat for behandling av masse av ved, og fremgangsmåte for bleking av masse
NZ235983A (en) * 1989-11-08 1993-01-27 Novo Nordisk As Process for hydrolysis of resins in lignocellulosic pulp using enzymes simultaneously with peroxy bleaching; ctmp fluff-pulp and absorbent articles produced therefrom
FI895501A (fi) * 1989-11-17 1991-05-18 Enso Gutzeit Oy Foerfarande foer tillverkning av massa.
FI92414B (fi) * 1989-11-27 1994-07-29 Enso Gutzeit Oy Menetelmä massan valmistamiseksi
FI85389C (fi) * 1989-12-12 1992-04-10 Enso Gutzeit Oy Foerfarande foer tillverkning av massa.
FI900544A (fi) * 1990-02-02 1991-08-03 Enso Gutzeit Oy Tutkimuskeskus Foerfarande foer tillverkning av massa.
DE4008893A1 (de) * 1990-03-20 1991-09-26 Call Hans Peter Verfahren zum enzymatischen bleichen von zellstoffen
DE4008894A1 (de) * 1990-03-20 1991-09-26 Call Hans Peter Verfahren zur altpapieraufbereitung mit enzymatischer druckfarbenentfernung
DK249990D0 (da) * 1990-10-17 1990-10-17 Novo Nordisk As Fremgangsmaade til enzymatisk pulpbehandling
EP0486125A1 (en) * 1990-11-13 1992-05-20 JAPAN PULP & PAPER RESEARCH INSTITUTE, INC. Lignocellulolytic composition, process of producing the same and use of the same
FI905954A (fi) * 1990-12-03 1992-06-04 Enso Gutzeit Oy Foerfarande foer blekning av cellulosamassa.
JPH04240287A (ja) * 1991-01-21 1992-08-27 Kobe Steel Ltd パルプの漂白方法
FI93230C (fi) * 1991-03-22 1995-03-10 Genencor Int Europ Menetelmä mekaanisen massan pihkavaikeuksien vähentämiseksi
AT400153B (de) * 1991-05-02 1995-10-25 Voest Alpine Ind Anlagen Verfahren zum bleichen von xylan- und lignocellulosehältigen materialien
DE4137761A1 (de) * 1991-05-17 1992-11-19 Call Hans Peter Verfahren zur delignifizierung von lignocellulosehaltigem material, bleiche und behandlung von abwaessern mittels laccasen mit erweiteter wirksamkeit
FI914780A0 (fi) * 1991-10-10 1991-10-10 Valtion Teknillinen Foerfarande foer entsymatisk behandling av lignocellulosahaltiga material, i synnerhet cellulosamassor.
CA2115881C (en) * 1993-02-25 2000-05-23 Michael G. Paice Non-chlorine bleaching of kraft pulp
JP3262646B2 (ja) * 1993-07-09 2002-03-04 日本製紙株式会社 パルプの漂白方法
SE505980C2 (sv) * 1993-12-23 1997-10-27 Bim Kemi Ab Sätt att förhindra peroxidnedbrytande enzymer vid blekning med väteperoxid
EP0879318B1 (en) 1996-02-08 2002-01-23 Novozymes A/S Process for increasing the negative charge on a lignocellulosic material and a modified lignocellulosic material with increased charge density
DE19820947B4 (de) * 1997-05-12 2005-12-01 Call, Krimhild Enzymatisches Bleichsystem mit neuen enzymwirkungsverstärkenden Verbindungen zum Verändern, Abbau oder Bleichen von Lignin, ligninhaltigen Materialien oder Verändern oder Abbau von Kohle sowie Verfahren unter Verwendung des Bleichsystems
US6824646B2 (en) 1999-03-23 2004-11-30 Oji Paper Co., Ltd. Process for oxygen bleaching and enzyme treating lignocellulosic pulp with liquid treatment and recovery
US6942754B2 (en) 1999-03-23 2005-09-13 Oji Paper Co., Ltd. Process for producing xylooligosaccharide from lignocellulose pulp

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1262117B (de) * 1964-05-05 1968-02-29 Aschaffenburger Zellstoffwerke Verfahren zur Kontrolle der Bleiche mit Chlordioxyd
FR1524581A (fr) * 1966-05-25 1968-05-10 Solvay Procédé de réglage de la blancheur d'une pâte cellulosique traitée par le peroxyde d'hydrogène ou un produit similaire
CA1232850A (en) * 1985-01-17 1988-02-16 Albert D. Friesen Purification of superoxide dismutase

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Abatract Bulletin of the Institute of Paper Chemistry, vol.57, No.7, January 1987, (Appleton, Wisconsin, US), M. Asther et al.: "Production of ligninolytic enzymes of Phanerochaete chrysosporium INA-12 in submerged agitated cultures", pages 956-957, abstract 8558 *
Abstract Bulletin of the Institute of Paper Chemistry, vol. 57, No. 7, January 1987, (Appleton, Wisconsin, US), P.J. Harvey et al.: "Lignin-degrading enzymes and the role of radical cations in lignin biodegradation", page 958, abstract 8575 *
Abstract Bulletin of the Institute of Paper Chemistry, vol. 57, No. 7, January 1987, (Appleton, Wisconsin, US), V.-B. Huynh et al.: "Oxidation of lignin model compounds by a manganese-dependent enzyme from phanerochaete chrysosporium as compared to chemically generated Mn(III)", page 959, abstract 8578 *
Tappi, vol. 61, No. 6, June 1978, B.I. Fleming et al.: "Soda pulping with anthraquinone. A mechanism", pages 43-46 *

Also Published As

Publication number Publication date
DK344888D0 (da) 1988-06-23
NO175104C (no) 1994-08-31
NO882808D0 (no) 1988-06-24
FI891909A (fi) 1989-04-21
WO1988003190A1 (en) 1988-05-05
JPH0718108B2 (ja) 1995-03-01
FI891909A0 (fi) 1989-04-21
NO882808L (no) 1988-06-24
DK344888A (da) 1988-06-23
AU8230387A (en) 1988-05-25
DK170810B1 (da) 1996-01-22
NO175104B (no) 1994-05-24
HU202938B (en) 1991-04-29
DE3636208A1 (de) 1988-05-05
EP0327576A1 (de) 1989-08-16
FI95289B (fi) 1995-09-29
HUT50894A (en) 1990-03-28
JPH02500990A (ja) 1990-04-05
ATE86318T1 (de) 1993-03-15
FI95289C (fi) 1996-01-10
DE3784515D1 (de) 1993-04-08
BR8707844A (pt) 1989-10-03
AU605215B2 (en) 1991-01-10

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